Classifications

• • H01M2/166—
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/463—Separators, membranes or diaphragms characterised by their shape
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/417—Polyolefins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/423—Polyamide resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/431—Inorganic material
  • H01M50/434—Ceramics
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/44—Fibrous material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/443—Particulate material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
  • H01M50/491—Porosity
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• nonaqueous electrolyte secondary battery porous layer for a nonaqueous electrolyte secondary battery (hereinafter referred to as “nonaqueous electrolyte secondary battery porous layer”).
• Nonaqueous electrolyte secondary batteries particularly lithium ion secondary batteries, have a high energy density and are therefore in wide use as batteries for personal computers, mobile phones, portable information terminals, and the like.
• Such nonaqueous electrolyte secondary batteries have recently been developed as on-vehicle batteries.
• a separator having excellent heat resistance As a member of such a nonaqueous electrolyte secondary battery, a separator having excellent heat resistance is under development.
• a separator which excels in heat resistance a separator including a porous layer which contains a heat-resistant component is known.
• Patent Literature 1 discloses a bursting strength of a nonwoven fabric for a separator in an alkaline battery.
• the separator including the porous layer as disclosed in Patent Literature 1 i.e., a conventional separator including a porous layer which contains a heat-resistant component is still insufficient in long-term battery characteristic.
• the present invention has aspects described in [1] through [11] below.
• a nonaqueous electrolyte secondary battery porous layer having a bursting strength of 3.0 kPa or more and 22.0 kPa or less.
• the nonaqueous electrolyte secondary battery porous layer described in [1] containing one or more resins selected from the group consisting of polyolefin, a (meth)acrylate resin, a fluorine-containing resin, a nitrogen-containing aromatic resin, a polyester resin, and a water-soluble polymer.
• the nonaqueous electrolyte secondary battery porous layer described in [1] containing a nitrogen-containing aromatic resin.
• the aramid resin is one or more aramid resins selected from the group consisting of poly(paraphenylene terephthalamide), poly(metaphenylene terephthalamide), and a paraphenylene terephthalamide/metaphenylene terephthalamide copolymer.
• the inorganic filler contains one or more inorganic substances selected from the group consisting of alumina, boehmite, aluminum hydroxide, magnesium hydroxide, magnesium oxide, titanium oxide, and silica.
• a nonaqueous electrolyte secondary battery laminated separator in which a nonaqueous electrolyte secondary battery porous layer described in any one of [1] through [9] is stacked on one surface or both surfaces of a polyolefin porous film.
• a nonaqueous electrolyte secondary battery including: a nonaqueous electrolyte secondary battery porous layer described in any one of [1] through [9]; or a nonaqueous electrolyte secondary battery laminated separator described in [10].
• the nonaqueous electrolyte secondary battery porous layer in accordance with an embodiment of the present invention advantageously makes it possible to provide a nonaqueous electrolyte secondary battery having an excellent long-term battery characteristic such as an AC resistance increase ratio at 1 kHz through 100 cycles.
• a nonaqueous electrolyte secondary battery porous layer (hereinafter, sometimes simply referred to as “porous layer”) in accordance with an embodiment of the present invention has a bursting strength of 3.0 kPa or more and 22.0 kPa or less.
• the nonaqueous electrolyte secondary battery porous layer in accordance with an embodiment of the present invention can solely constitute a separator for a nonaqueous electrolyte secondary battery (hereinafter referred to as a “nonaqueous electrolyte secondary battery separator”).
• the nonaqueous electrolyte secondary battery porous layer in accordance with an embodiment of the present invention can be stacked on at least one surface of a polyolefin porous film (hereinafter sometimes simply referred to as “porous film”) so as to constitute a laminated separator for a nonaqueous electrolyte secondary battery (hereinafter referred to as a “nonaqueous electrolyte secondary battery laminated separator” or simply as “laminated separator”) which will be described later.
• a polyolefin porous film hereinafter sometimes simply referred to as “porous film”
• a “bursting strength” in accordance with an embodiment of the present invention is measured by a method called “Mullen method”.
• the “bursting strength” is measured as follows: that is, a thin film is fixed to a surface of a rubber balloon, i.e., a swelling rubber surface (rubber diaphragm), and then the rubber balloon is swollen and a magnitude of stress which is applied when the thin film bursts is measured as the “bursting strength”. In that case, the rubber balloon swells under the thin film which is a measurement target object, and thus stresses are applied to the thin film from all directions.
• a “tensile strength” is generally used in measuring strength of a thin film and the “tensile strength” is a parameter for evaluating strength and elasticity with respect to a stress that is applied from a single direction.
• the “bursting strength” is a parameter for evaluating strength and elasticity with respect to stresses applied from all directions.
• the “bursting strength” can be adjusted by controlling elasticity of a resin and a filler themselves which are components constituting the porous layer in accordance with an embodiment of the present invention and controlling a weight per unit area of the porous layer.
• an electrode typically, a negative electrode
• a porous layer included in a nonaqueous electrolyte secondary battery separator or in a nonaqueous electrolyte secondary battery laminated separator.
• the “bursting strength” can be used to evaluate, in an aspect close to an actual nonaqueous electrolyte secondary battery, strength and elasticity of a porous layer included in a nonaqueous electrolyte secondary battery with respect to stresses applied from all directions to the porous layer when charge-discharge cycles are repeated.
• the porous layer in accordance with an embodiment of the present invention has the “bursting strength” which is 3.0 kPa or more. From this, it is possible to inhibit the porous layer and the nonaqueous electrolyte secondary battery laminated separator including the porous layer from being deteriorated and deformed by stresses applied to the porous layer due to expansion of the electrode, i.e., by pressure with respect to the porous layer applied due to expansion of the electrode. As a result, it is possible to improve a battery performance such as a long-term battery characteristic of the nonaqueous electrolyte secondary battery after charge-discharge cycles are repeated.
• the “bursting strength” of the porous layer in accordance with an embodiment of the present invention is preferably 5.0 kPa or more, more preferably 10.0 kPa or more.
• the electrode repeats expansion and contraction in accordance with the charge-discharge cycles.
• the porous layer In a case where the porous layer is excessively stretched due to expansion of the electrode and then the electrode contracts, the porous layer cannot follow the contraction of the electrode and therefore the porous layer and the nonaqueous electrolyte secondary battery laminated separator including the porous layer may become flaccid. As a result, uniformity in ion permeation through the porous layer and the nonaqueous electrolyte secondary battery laminated separator may be deteriorated, and therefore the battery performance of the nonaqueous electrolyte secondary battery may be lowered.
• the porous layer in accordance with an embodiment of the present invention has the “bursting strength” which is 22.0 kPa or less. From this, it is possible to inhibit generation of the above described flaccid state, and to improve uniformity in ion permeation through the porous layer and the nonaqueous electrolyte secondary battery laminated separator. As a result, it is possible to improve a battery performance such as a long-term battery characteristic of the nonaqueous electrolyte secondary battery. From the above point of view, the “bursting strength” of the porous layer in accordance with an embodiment of the present invention is preferably 20.0 kPa or less, more preferably 18.0 kPa or less.
• the “bursting strength” can be 5.0 kPa or more and 20.0 kPa or less, or can be 10.0 kPa or more and 18.0 kPa or less.
• the “bursting strength” of the porous layer can be calculated by, for example, (i) measuring a bursting strength of the nonaqueous electrolyte secondary battery laminated separator in which the porous layer is stacked on one surface of a polyolefin porous film, (ii) measuring a bursting strength of only the polyolefin porous film which is obtained by eliminating the porous layer from the nonaqueous electrolyte secondary battery laminated separator, and then (iii) subtracting the bursting strength of only the polyolefin porous film from the bursting strength of the nonaqueous electrolyte secondary battery laminated separator.
• the “bursting strength” of the porous layer can also be calculated by, for example, (a) measuring a bursting strength of only the polyolefin porous film, (b) measuring a bursting strength of the nonaqueous electrolyte secondary battery laminated separator in which the porous layer is stacked on one surface of the polyolefin porous film, and (c) subtracting the bursting strength of the polyolefin porous film from the bursting strength of the nonaqueous electrolyte secondary battery laminated separator.
• the “bursting strength” is measured by using, for example, an automatic Mullen bursting strength tester such as IT-MBDA available from INTEC CO., LTD.
• the nonaqueous electrolyte secondary battery laminated separator is preferably set in the automatic Mullen bursting strength tester such that a surface of the porous layer in the nonaqueous electrolyte secondary battery laminated separator is arranged on a rubber diaphragm side.
• the porous layer in accordance with an embodiment of the present invention can be provided, as a member included in a nonaqueous electrolyte secondary battery, between (i) the polyolefin porous film and (ii) at least one of a positive electrode and a negative electrode.
• the porous layer can be formed on at least one surface of the polyolefin porous film.
• the porous layer can be formed on an active material layer of at least one of the positive electrode and the negative electrode.
• the porous layer can be provided between the polyolefin porous film and at least one of the positive electrode and the negative electrode in such a manner as to be in contact with the polyolefin porous film and with the at least one of the positive electrode and the negative electrode.
• the porous layer is preferably stacked on a surface of the porous film which surface faces the positive electrode.
• the porous layer is more preferably stacked so as to make contact with the positive electrode.
• the porous layer is preferably an insulating porous layer.
• the porous layer in accordance with an embodiment of the present invention has a structure in which many pores, connected to one another, are provided, so that the porous layer is a layer through which a gas or a liquid can pass from one surface to the other.
• the porous layer can be a layer which serves as an outermost layer of the laminated separator and comes into contact with an electrode.
• the porous layer in accordance with an embodiment of the present invention is typically a resin layer containing a resin. It is preferable that the resin is insoluble in the electrolyte of the battery and is electrochemically stable when the battery is in normal use.
• Examples of the resin used in the porous layer in accordance with an embodiment of the present invention include polyolefins; (meth)acrylate resins; fluorine-containing resins; nitrogen-containing aromatic resins; polyester resins; rubbers; resins having a melting point or glass transition temperature of not lower than 180° C.; water-soluble polymers; polycarbonate, polyacetal, and polyether ether ketone.
• polyolefins polyolefins, (meth)acrylate resins, fluorine-containing resins, nitrogen-containing aromatic resins, polyester resins and water-soluble polymers are preferable.
• the polyolefins are preferably polyethylene, polypropylene, polybutene, an ethylene/propylene copolymer, and the like.
• fluorine-containing resins encompass polyvinylidene fluoride, polytetrafluoroethylene, a vinylidene fluoride/hexafluoropropylene copolymer, a tetrafluoroethylene/hexafluoropropylene copolymer, a tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, a vinylidene fluoride/tetrafluoroethylene copolymer, a vinylidene fluoride/trifluoroethylene copolymer, a vinylidene fluoride/trichloroethylene copolymer, a vinylidene fluoride/vinyl fluoride copolymer, a vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene copolymer, and an ethylene/tetrafluoroethylene copolymer.
• fluorine-containing resins encompass fluorine-containing rubber
• the nitrogen-containing aromatic resin is preferably one or more resins selected from the group consisting of an aramid resin, aromatic polyamide imide, and aromatic polyimide.
• the aramid resin includes aromatic polyamide, wholly aromatic polyamide, and the like.
• the aromatic polyamide is preferably one or more resins selected from the group consisting of para(p)-aromatic polyamide and meth(m)-aromatic polyamide.
• aramid resins include poly(paraphenylene terephthalamide), poly(metaphenylene isophthalamide), poly(metaphenylene terephthalamide), poly(parabenzamide), poly(metabenzamide), poly(4,4′-benzanilide terephthalamide), poly(paraphenylene-4,4′-biphenylene dicarboxylic acid amide), poly(metaphenylene-4,4′-biphenylene dicarboxylic acid amide), poly(paraphenylene-2,6-naphthalene dicarboxylic acid amide), poly(metaphenylene-2,6-naphthalene dicarboxylic acid amide), poly(2-chloroparaphenylene terephthalamide), a paraphenylene terephthalamide/metaphenylene terephthalamide copolymer, a paraphenylene terephthalamide/2,6-dichloroparaphenylene terephthalamide copolymer, and a
• the polyester resins are preferably aromatic polyesters such as polyarylates, and liquid crystal polyesters.
• the rubbers include a styrene/butadiene copolymer and a hydride thereof, a methacrylate ester copolymer, an acrylonitrile/acrylic ester copolymer, a styrene/acrylic ester copolymer, ethylene propylene rubber, and polyvinyl acetate.
• Examples of the resins each having a melting point or a glass transition temperature of not lower than 180° C. include polyphenylene ether, polysulfone, polyether sulfone, polyphenylene sulfide, polyetherimide, polyamide imide, and polyether amide.
• water-soluble polymers examples include polyvinyl alcohol, polyethylene glycol, cellulose ether, sodium alginate, polyacrylic acid, polyacrylamide, and polymethacrylic acid.
• Each of these resins contained in the porous layer can be used solely. Alternatively, two or more of these resins contained in the porous layer can be used in combination.
• the porous layer in accordance with an embodiment of the present invention can contain particles.
• the resin is to have a function of a binder resin.
• the particles are organic particles or inorganic particles which are generally referred to as a filler.
• the particles are preferably a heat-resistant filler.
• the heat-resistant filler can be an inorganic filler or a heat-resistant organic filler, and preferably contains an inorganic filler.
• the heat-resistant filler means a filler having a melting point of not lower than 150° C.
• organic substances constituting the organic particles contained in the porous layer in accordance with an embodiment of the present invention include (i) a homopolymer of a monomer such as styrene, vinyl ketone, acrylonitrile, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, or methyl acrylate, or (ii) a copolymer of two or more of such monomers; fluorine-containing resins such as polytetrafluoroethylene, an ethylene tetrafluoride/propylene hexafluoride copolymer, a tetrafluoroethylene/ethylene copolymer, and polyvinylidene fluoride; a melamine resin; a urea resin; polyethylene; polypropylene; polyacrylic acid and polymethacrylic acid; a resorcinol resin; and the like.
• the organic particles can contain a single kind
• the resorcinol resin can be, specifically, resorcin (resorcinol), and a polymer obtained by polymerizing resorcin and an aldehyde monomer.
• the aldehyde monomer can be any aldehyde. Examples of the aldehyde monomer include formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, furfural, thiophene carboxaldehyde, and the like.
• the aldehyde monomer is preferably formaldehyde.
• a formaldehyde monomer can be prepared from trioxane (which is a trimer of formaldehyde) or paraformaldehyde (which is a multimer of formaldehyde) in polymerization reaction of resorcin and the formaldehyde monomer.
• trioxane which is a trimer of formaldehyde
• paraformaldehyde which is a multimer of formaldehyde
• a single kind of aldehyde monomer or a mixture of two or more kinds of aldehyde monomers can be used.
• the inorganic particles contained in the porous layer in accordance with an embodiment of the present invention include inorganic fillers each made of an inorganic substance such as calcium carbonate, talc, clay, kaolin, silica, hydrotalcite, diatomaceous earth, magnesium carbonate, barium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, aluminum hydroxide, boehmite, magnesium hydroxide, calcium oxide, magnesium oxide, titanium oxide, titanium nitride, alumina (aluminum oxide), aluminum nitride, mica, zeolite, or glass.
• the inorganic filler can be (i) only one kind of filler or (ii) two or more kinds of fillers in combination.
• the inorganic filler is preferably an inorganic filler made of a metal oxide or an inorganic filler made of a metal hydroxide.
• the inorganic filler made of a metal oxide can be, for example, an inorganic filler made of an aluminum oxide and/or a magnesium oxide.
• the inorganic filler made of a metal hydroxide can be, for example, an inorganic filler made of an aluminum hydroxide and/or a magnesium hydroxide.
• An average particle diameter (D50) of the filler is preferably 0.001 ⁇ m or more and 10 ⁇ m or less, more preferably 0.01 ⁇ m or more and 8 ⁇ m or less, further preferably 0.05 ⁇ m or more and 5 ⁇ m or less.
• the average particle diameter of the filler is a value measured with use of MICROTRAC (MODEL: MT-3300EXII) available from NIKKISO CO., LTD.
• a shape of the filler varies depending on a method for producing a raw material, i.e., an organic substance or an inorganic substance, a dispersion condition of the filler in preparing a coating liquid for forming the porous layer, and the like.
• the shape of the filler can be any of various shapes including (i) a shape such as a spherical shape, an oval shape, a rectangular shape, a gourd-like shape and (ii) an indefinite shape having no specific shape.
• a contained amount of the filler is preferably 40% by volume to 99% by volume, more preferably 45% by volume to 95% by volume.
• the contained amount of the filler falls within the above range, it is less likely that a void, which is formed when the fillers come into contact with each other, is blocked by the resin or the like, and this makes it possible to obtain sufficient ion permeability.
• the contained amount falling within the above range also makes it possible to set a weight per unit area to an appropriate value.
• the porous layer can contain two or more kinds of particles in combination which two or more kinds differ from each other in particle diameter or in specific surface area.
• the porous layer in accordance with an embodiment of the present invention preferably contains a heat-resistant filler.
• heat resistance means that a melting point is not lower than 150° C.
• the heat-resistant filler can be one kind of heat-resistant filler or can be a combination of two or more kinds of heat-resistant fillers.
• the heat-resistant filler is preferably the above described inorganic filler, a heat-resistant organic filler, or a mixture thereof.
• the heat-resistant filler preferably contains the above described inorganic filler.
• the heat-resistant organic filler is preferably a thermosetting resin filler, a heat-resistant thermoplastic resin filler, or a mixture thereof.
• a resin constituting the heat-resistant organic filler is preferably the above described aramid resin or the above described resorcinol resin.
• the aramid resin is preferably poly(paraphenylene terephthalamide), poly(metaphenylene terephthalamide), or the paraphenylene terephthalamide/metaphenylene terephthalamide copolymer.
• the porous layer in accordance with an embodiment of the present invention can contain a component different from the resin and the particles.
• the other component include a surfactant, a wax, and the like.
• a content of that other component is preferably 0% by weight to 10% by weight with respect to the total weight of the porous layer.
• a thickness of the porous layer in accordance with an embodiment of the present invention is preferably 5 ⁇ m or less per layer, more preferably 4 ⁇ m or less per layer, from the viewpoint of preventing a deterioration in battery characteristic.
• the thickness of the porous layer is preferably 0.5 ⁇ m or more per layer, more preferably 1 ⁇ m or more per layer, from the viewpoint of sufficiently preventing internal short circuit caused due to breakage of the battery or the like and of preventing a decrease in retained amount of the electrolyte.
• the porous layer in accordance with an embodiment of the present invention preferably has a sufficiently porous structure.
• the porous layer preferably has a porosity of 30% to 60%.
• the porosity can be calculated by, for example, the following formula (1), where (i) W is a weight (g) of a porous layer having a certain volume (8 cm ⁇ 8 cm ⁇ d (cm) (d: thickness)), (ii) d is the thickness ( ⁇ m) of the porous layer, and (iii) ⁇ is an absolute specific gravity (g/cm 3 ) of the porous layer:
• the porous layer in accordance with an embodiment of the present invention preferably has an average pore diameter which falls within a range from 20 nm to 100 nm, from the viewpoint of ion permeability and of preventing particles from intruding into the positive electrode and the negative electrode.
• the average pore diameter can be calculated by, for example, (i) observing the porous layer in accordance with an embodiment of the present invention from an upper surface with use of a scanning electron microscope (SEM), (ii) measuring respective pore diameters of a plurality of holes randomly selected, and (iii) obtaining an average value of the pore diameters thus measured.
• SEM scanning electron microscope
• a weight per unit area of the porous layer in accordance with an embodiment of the present invention is preferably 0.5 g/m 2 to 10 g/m 2 , more preferably 0.5 g/m 2 to 5 g/m 2 per layer of the porous layer in view of strength, thickness, weight, and handleability of the porous layer.
• the bursting strength of the porous layer in accordance with an embodiment of the present invention partially correlates with a weight per unit area of the same porous layer (i.e., provided that materials and component compositions are the same).
• a weight per unit area of the porous layer in accordance with an embodiment of the present invention is preferably 0.5 g/m 2 to 4.6 g/m 2 , more preferably 1.0 g/m 2 to 3.0 g/m 2 .
• a method for producing the porous layer in accordance with an embodiment of the present invention can be, for example, a method which includes any one of processes (1) through (3) below and in which a porous layer is formed on a base material.
• a coating liquid in the processes (1) through (3) below typically contains the above described resin and, if needed, can contain the above described particles, as components constituting the porous layer in accordance with an embodiment of the present invention.
• the resin deposited is further dried for removal of the solvent, and thus a porous layer can be produced.
• the particles can be dispersed and the resin can be dissolved.
• the base material is not particularly limited and encompasses, for example, a positive electrode, a negative electrode, and a porous film which serves as a base material of the laminated separator in accordance with an embodiment of the present invention.
• the solvent can be regarded as a solvent in which the resin is dissolved and as a dispersion medium in which the resin or the particles are dispersed.
• the solvent for the coating liquid is preferably a solvent that does not adversely affect the base material, that allows the resin to be dissolved or dispersed therein uniformly and stably, and that allows the particles to be dispersed therein uniformly and stably.
• the solvent include N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, acetone, alcohols, water, and a mixed solvent containing two or more of these.
• the deposition solvent is preferably isopropyl alcohol or t-butyl alcohol, for example.
• the low-boiling-point organic acid can be, for example, paratoluene sulfonic acid or acetic acid.
• the above preferable production method can be a method in which the coating liquid is left still before coating so that the coating liquid has a dispersion state which is moderately nonuniform.
• a period of time for which the coating liquid is left still before coating is preferably 10 minutes to 2 hours, more preferably 45 minutes to 1 hour and 15 minutes.
• the coating liquid has a dispersion state which is moderately nonuniform, it is possible to form a porous layer in which uniformities of the resin and particles are moderately disturbed, and it is possible to adjust a contact area between the resin and the particles in the porous layer. As a result, it is possible to obtain the porous layer which has moderate elasticity and a bursting strength that has been adjusted to fall within a preferably range.
• the nonaqueous electrolyte secondary battery laminated separator in accordance with an embodiment of the present invention has a configuration in which the porous layer is stacked on at least one surface of a polyolefin porous film.
• the porous layer in accordance with an embodiment of the present invention only needs to be at least of the porous layers, and it is preferable that the porous layer in accordance with an embodiment of the present invention is stacked on one surface of the polyolefin porous film, and another porous layer is stacked on the other surface of the polyolefin porous film.
• the polyolefin porous film in accordance with an embodiment of the present invention includes polyolefin as a main component.
• the polyolefin porous film has therein many pores, connected to one another, so that a gas and a liquid can pass through the polyolefin porous film from one side to the other side.
• the porous film serves as a base material on which the porous layer is stacked in the laminated separator in accordance with an embodiment of the present invention.
• the laminated separator in accordance with an embodiment of the present invention can include, in addition to the porous film and the porous layer, other layer(s) such as an adhesive layer, a heat-resistant layer, and/or a protective layer.
• the porous film contains a polyolefin at a proportion of not less than 50% by volume, preferably not less than 90% by volume, more preferably not less than 95% by volume, relative to the entire porous film.
• the polyolefin more preferably contains a high molecular weight component having a weight-average molecular weight of 5 ⁇ 10 5 to 15 ⁇ 10 6 .
• the polyolefin more preferably contains a high molecular weight component having a weight-average molecular weight of not less than 1,000,000 because such a polyolefin allows the nonaqueous electrolyte secondary battery separator to have higher strength.
• polyolefin thermoplastic resin
• polyolefin thermoplastic resin
• polyolefin thermoplastic resin
• polyolefin thermoplastic resin
• homopolymer polyethylene, polypropylene, and polybutene
• copolymer examples include an ethylene/propylene copolymer.
• polyethylene is more preferable as it is capable of preventing a flow of an excessively large electric current at a lower temperature.
• the prevention of an excessively large electric current is also referred to as shutdown.
• the polyethylene include low-density polyethylene, high-density polyethylene, linear polyethylene (ethylene/ ⁇ -olefin copolymer), and ultra-high molecular weight polyethylene having a weight-average molecular weight of not less than 1,000,000.
• ultra-high molecular weight polyethylene having a weight-average molecular weight of not less than 1,000,000 is further preferable.
• the porous film has a film thickness of preferably 4 ⁇ m to 40 ⁇ m, more preferably 5 ⁇ m to 30 ⁇ m, still more preferably 6 ⁇ m to 15 ⁇ m.
• the porous film can have a weight per unit area which weight is appropriately determined in view of the strength, film thickness, weight, and handleability.
• the weight per unit area is, however, within a range of preferably 4 g/m 2 to 15 g/m 2 , more preferably 4 g/m 2 to 12 g/m 2 , even more preferably 5 g/m 2 to 10 g/m 2 , so as to allow a nonaqueous electrolyte secondary battery to have a higher weight energy density and a higher volume energy density.
• the porous film has an air permeability of preferably 30 sec/100 mL to 500 sec/100 mL, more preferably 50 sec/100 mL to 300 sec/100 mL, in terms of Gurley values.
• a porous film having an air permeability within the above range can have sufficient ion permeability.
• a laminated separator in which the porous layer described above is provided on a porous film has an air permeability of preferably 30 sec/100 mL to 1000 sec/100 mL, more preferably 50 sec/100 mL to 800 sec/100 mL in terms of Gurley values.
• the laminated separator which has the above air permeability, allows the nonaqueous electrolyte secondary battery to have sufficient ion permeability.
• the porous film has a porosity of preferably 20% by volume to 80% by volume, more preferably 30% by volume to 75% by volume, so as to (i) retain a larger amount of electrolyte and (ii) obtain the function of reliably preventing a flow of an excessively large electric current at a lower temperature. Further, in order to obtain sufficient ion permeability and prevent particles from entering the positive electrode and/or the negative electrode, the porous film has pores each having a pore diameter of preferably not larger than 0.30 ⁇ m, more preferably not larger than 0.14 ⁇ m, even more preferably not larger than 0.10 ⁇ m.
• the method for producing the polyolefin porous film is not limited to any particular one.
• the method can include the following steps:
• a method for producing the nonaqueous electrolyte secondary battery laminated separator in accordance with an embodiment of the present invention can be, for example, the above-described method for producing the porous layer in which the above-described polyolefin porous film is used as a base material which is coated with the coating liquid.
• a nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention includes (i) a nonaqueous electrolyte secondary battery porous layer in accordance with an embodiment of the present invention or (ii) a nonaqueous electrolyte secondary battery laminated separator in accordance with an embodiment of the present invention.
• the nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention can be, for example, a nonaqueous secondary battery that achieves an electromotive force through doping with and dedoping of lithium, and can be a lithium-ion secondary battery that includes a member for a nonaqueous electrolyte secondary battery (hereinafter referred to as a “nonaqueous electrolyte secondary battery member”) including a positive electrode, a porous layer in accordance with an embodiment of the present invention, a polyolefin porous film, and a negative electrode, which are stacked in this order, that is, a nonaqueous electrolyte secondary battery member including a positive electrode, a nonaqueous electrolyte secondary battery laminated separator in accordance with an embodiment of the present invention, and a negative electrode, which are stacked in this order.
• constituent elements of the nonaqueous electrolyte secondary battery other than the porous layer are not limited to those described below.
• the nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention is typically configured so that a battery element is enclosed in an exterior member, the battery element including (i) a structure in which the negative electrode and the positive electrode face each other through the nonaqueous electrolyte secondary battery porous layer in accordance with an embodiment of the present invention or the nonaqueous electrolyte secondary battery laminated separator in accordance with an embodiment of the present invention and (ii) an electrolyte with which the structure is impregnated.
• the nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention is preferably a secondary battery including a nonaqueous electrolyte, and is particularly preferably a lithium-ion secondary battery.
• the nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention includes the nonaqueous electrolyte secondary battery porous layer in accordance with an embodiment of the present invention having the bursting strength of 3.0 kPa or more and 22.0 kPa or less, and therefore brings about an effect of having an excellent long-term battery characteristic.
• Examples of a positive electrode included in the nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention encompass a positive electrode sheet having a structure in which an active material layer including a positive electrode active material and a binding agent is formed on a current collector.
• the active material layer can further contain an electrically conductive agent.
• the positive electrode active material is, for example, a material capable of being doped with and dedoped of lithium ions.
• Examples of such a material encompass a lithium complex oxide containing at least one transition metal such as V, Mn, Fe, Co, or Ni.
• Examples of the electrically conductive agent encompass carbonaceous materials such as natural graphite, artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fiber, and a fired product of an organic polymer compound. It is possible to use (i) only one kind of the above electrically conductive agents or (ii) two or more kinds of the above electrically conductive agents in combination, for example, a mixture of artificial graphite and carbon black.
• binding agent encompass: thermoplastic resins such as polyvinylidene fluoride, a copolymer of vinylidene fluoride, polytetrafluoroethylene, a vinylidene fluoride/hexafluoropropylene copolymer, a tetrafluoroethylene/hexafluoropropylene copolymer, a tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, an ethylene/tetrafluoroethylene copolymer, a vinylidene fluoride/tetrafluoroethylene copolymer, a vinylidene fluoride/trifluoroethylene copolymer, a vinylidene fluoride/trichloroethylene copolymer, a vinylidene fluoride/vinyl fluoride copolymer, a vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene copolymer, a thermoplastic
• the positive electrode mix can be prepared by, for example, a method of applying pressure to the positive electrode active material, the electrically conductive agent, and the binding agent on the positive electrode current collector or a method of using an appropriate organic solvent so that the positive electrode active material, the electrically conductive agent, and the binding agent are made into a paste form.
• Examples of the positive electrode current collector encompass electric conductors such as Al, Ni, and stainless steel.
• Al is preferable because Al is easily processed into a thin film and is inexpensive.
• the positive electrode sheet can be produced, that is, the positive electrode mix can be supported by the positive electrode current collector by, for example, a method in which pressure is applied to the positive electrode active material, the electrically conductive agent, and the binding agent on the positive electrode current collector to form a positive electrode mix thereon.
• Examples of a negative electrode included in the nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention encompass a negative electrode sheet having a structure in which an active material layer including a negative electrode active material and a binding agent is formed on a current collector.
• the active material layer can further contain an electrically conductive agent.
• the negative electrode active material encompass (i) a material capable of being doped with and dedoped of lithium ions, (ii) a lithium metal, and (iii) a lithium alloy.
• Specific examples of the material encompass: (1) carbonaceous materials such as natural graphite, artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fiber, and a fired product of an organic polymer compound; (2) chalcogen compounds such as an oxide and a sulfide that are doped with and dedoped of lithium ions at an electric potential lower than that for the positive electrode; (3) metals such as aluminum (Al), lead (Pb), tin (Sn), bismuth (Bi), or silicon (Si), each of which is alloyed with alkali metal; (4) an intermetallic compound (AlSb, Mg 2 Si, NiSi 2 ) of a cubic system in which intermetallic compound alkali metal can be inserted in voids in a lattice; and (5) lithium nitrogen
• the negative electrode mix can be prepared by, for example, a method in which pressure is applied to the negative electrode active material on a negative electrode current collector or a method in which an appropriate organic solvent is used so that the negative electrode active material is made into a paste form.
• Examples of the negative electrode current collector encompass electric conductors such as Cu, Ni, and stainless steel.
• the negative electrode sheet can be produced, that is, the negative electrode mix can be supported by the negative electrode current collector by, for example, a method in which pressure is applied to the negative electrode active material on the negative electrode current collector to form a negative electrode mix thereon.
• the above paste preferably includes the above electrically conductive agent and the above binding agent.
• a nonaqueous electrolyte for use in the nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention is a nonaqueous electrolyte generally used in a nonaqueous electrolyte secondary battery, and is not limited to any particular one.
• nonaqueous electrolyte encompass a nonaqueous electrolyte prepared by dissolving a lithium salt in an organic solvent.
• the lithium salt encompass LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN(CF 3 SO 2 ) 2 , LiC(CF 3 SO 2 ) 3 , Li 2 B 10 Cl 10 , lower aliphatic carboxylic acid lithium salt, and LiAlCl 4 . It is possible to use only one kind of the above lithium salts or two or more kinds of the above lithium salts in combination.
• organic solvent in the nonaqueous electrolyte in accordance with an embodiment of the present invention include carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-trifluoromethyl-1,3-dioxolane-2-on, and 1,2-di(methoxy carbonyloxy)ethane; ethers such as 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methylether, 2,2,3,3-tetrafluoropropyl difluoro methylether, tetrahydrofuran, and 2-methyl tetrahydrofuran; esters such as methyl formate, methyl acetate, and ⁇ -butyrolactone; nitriles such as acetonitrile and butyronitrile; amides such as N,N-dimethylformamide and N,N-dimethylacetamide;
• a nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention can be produced by, for example, (i) producing a nonaqueous electrolyte secondary battery member by providing the positive electrode, the nonaqueous electrolyte secondary battery laminated separator in accordance with an embodiment of the present invention, and a negative electrode in this order, then (ii) inserting the nonaqueous electrolyte secondary battery member into a container that will serve as a housing of a nonaqueous electrolyte secondary battery, then (iii) filling the container with a nonaqueous electrolyte, and then (iv) hermetically sealing the container while reducing pressure inside the container.
• the nonaqueous electrolyte secondary battery is not particularly limited in shape and can have any shape such as the shape of a thin plate (sheet), a disk, a cylinder, or a prism such as a cuboid.
• the nonaqueous electrolyte secondary battery member and the nonaqueous electrolyte secondary battery can each be produced by any method, and can each be produced by a conventionally publicly known method.
• the present invention is not limited to the embodiments, but can be altered variously by a skilled person in the art within the scope of the claims.
• the present invention also encompasses, in its technical scope, any embodiment derived by appropriately combining technical means disclosed in differing embodiments. Further, it is possible to form a new technical feature by combining the technical means disclosed in the respective embodiments.
• a thickness of the nonaqueous electrolyte secondary battery laminated separator i.e., a total film thickness
• a thickness of the layer A i.e., a thickness of the layer A
• a thickness of the layer B were each measured with use of a high-precision digital length measuring machine available from Mitutoyo Corporation.
• Weight per unit area (g/m 2 ) W /(0.064 ⁇ 0.04)
• the weight per unit area of the layer A was calculated in a similar manner.
• the weight per unit area of the layer B was calculated by subtracting the weight per unit area of the layer A from the weight per unit area of the nonaqueous electrolyte secondary battery laminated separator.
• the average particle diameter and the particle size distribution of the filler were measured with use of MICROTRAC (MODEL: MT-3300EXII) available from NIKKISO CO., LTD.
• bursting strengths of nonaqueous electrolyte secondary battery laminated separators produced in Examples 1 through 4 and Comparative Examples 1 and 2 and a bursting strength of a porous film (layer A) itself included in each of the nonaqueous electrolyte secondary battery laminated separators were measured under conditions indicated below.
• the nonaqueous electrolyte secondary battery laminated separator was set in the automatic Mullen bursting strength tester such that a surface of a porous layer (layer B) comes on a rubber diaphragm side, and bursting strengths of the nonaqueous electrolyte secondary battery laminated separator and the layer A were measured in that setting.
• Test method In conformity to the method of JIS L 1096 8.1 A
• Test environment Room temperature at 20 ⁇ 2° C., indoor humidity at 60 ⁇ 5% RH
• a bursting strength of the layer B was calculated based on a formula (2) below.
• Bursting strength (kPa) of layer B bursting strength (kPa) of nonaqueous electrolyte secondary battery laminated separator ⁇ bursting strength (kPa) of layer A only (2)
• a measurement sample having a size of 15.0 cm ⁇ 15.0 cm was cut out.
• a bursting strength of the nonaqueous electrolyte secondary battery laminated separator was measured.
• a bursting strength of only the porous film (layer A) was measured.
• a bursting strength of a porous layer in the measurement sample was calculated as a bursting strength of the porous layer (layer B).
• a voltage having an amplitude of 10 mV was applied to the prepared nonaqueous electrolyte secondary battery at a room temperature of 25° C. with use of an LCR meter (product name: Chemical Impedance Meter, Model: 3532-80) available from HIOKI E.E. CORPORATION, and thus a Nyquist plot of the nonaqueous electrolyte secondary battery was prepared.
• a size of an X intercept in the Nyquist plot was read as a resistance RikHz of a real part at a measuring frequency of 1 kHz.
• RikHz is a half of electrode resistance.
• the value RikHz thus measured is defined as “AC resistance at 1 kHz”.
• a nonaqueous electrolyte secondary battery laminated separator 1 was prepared with use of a layer A and a layer B below.
• a porous film serving as a base material was prepared with use of polyethylene which is polyolefin.
• the polyethylene resin composition was rolled with use of a pair of rollers each having a surface temperature of 150° C., so that a sheet was prepared.
• This sheet was immersed in an aqueous hydrochloric acid solution (containing 4 mol/L of hydrochloric acid and 0.5% by weight of nonionic surfactant) for dissolving and removal of the calcium carbonate.
• the sheet was stretched at a stretching temperature of 105° C. and a stretching magnification of 6 times, and thus a porous film (layer A) made of polyethylene was prepared.
• resorcin and 340.89 g of a 37% aqueous formaldehyde solution were put into a 2-L separable flask in which air had been replaced with nitrogen so that a molar ratio of resorcin and formaldehyde became 1:3. Further, 1541.5 g of water and 0.0786 g of sodium carbonate were added. A dispersion state was made uniform by stirring and then a temperature was raised to 80° C. The mixture was kept at 80° C. for 24 hours to carry out polymerization reaction, and thus a suspension containing particles of a resorcin-formalin resin (RF resin) was obtained.
• RF resin resorcin-formalin resin
• the suspension thus obtained was centrifuged, so that the particles of the RF resin precipitated. Then, a supernatant dispersion medium was removed while the precipitated particles of the RF resin were left. Then, the RF resin was cleaned by carrying out twice a cleaning operation including (i) adding water which served as a cleaning liquid, (ii) stirring a resulting mixture, and (iii) centrifuging the mixture so as to remove the cleaning liquid. That is, the cleaning operation was carried out twice in total. Particles of the cleaned RF resin were dried, and an organic filler (1) (D50: 1.0 ⁇ m) was quantitatively synthesized. As a binder resin, sodium carboxymethylcellulose (CMC) (available from DAICEL CORPORATION; CMC1110) was used.
• CMC carboxymethylcellulose
• the organic filler (1), CMC, and the solvent were mixed so that a solid concentration, that is, a total concentration of the organic filler (1) and CMC became 20.0% by weight and a weight ratio of organic filler (1):CMC became 100:3, and thus a coating liquid 1 was prepared.
• the coating liquid 1 was left still for 1 hour at a room temperature, so that a dispersion state of components in the coating liquid 1 became moderately nonuniform.
• One surface of the layer A was coated, by use of a gravure coater, with the coating liquid 1 which had been left still for 1 hour, and then dried to deposit the binder resin, i.e., CMC contained in the coating liquid 1.
• CMC binder resin contained in the coating liquid 1.
• a laminated porous film 1 in which the layer B was stacked on the surface of the layer A was obtained.
• the laminated porous film 1 thus obtained is herein referred to as a nonaqueous electrolyte secondary battery laminated separator 1.
• a nonaqueous electrolyte secondary battery laminated separator 2 was prepared with use of a layer A and a layer B below.
• a polyethylene porous film (layer A) was prepared by an operation similar to that of Example 1.
• NMP N-methyl-2-pyrrolidone
• the temperature of a resultant solution was brought down to a room temperature, and then 68.23 g of paraphenylenediamine (hereinafter, referred to as “PPD”) was added to and completely dissolved in a resultant mixture. While a temperature of a resultant solution was maintained at 20° C. ⁇ 2° C. and a dissolved oxygen concentration in polymerization was maintained at 0.5%, 124.97 g of dichloride terephthalate (hereinafter, referred to as “TPC”), which was separated into 10 pieces, was one-by-one added to the solution at approximately 5-minute intervals. After that, a resultant solution was ripened for 1 hour while being stirred and maintained at 20° C. ⁇ 2° C. Then, the solution thus ripened was filtered through 1500-mesh stainless steel gauze. The solution thus obtained was a para-aramid solution having a para-aramid concentration of 6%.
• PPD paraphenylenediamine
• the para-aramid solution thus obtained was weighed by 100 g and put in a flask. Then, 300 g of NMP was added to the solution. Thus, a para-aramid solution having a para-aramid concentration of 1.5% by weight was prepared, and the solution thus prepared was stirred for 60 minutes. Subsequently, 3 g of fine powdery alumina (available from NIPPON AEROSIL CO., LTD., alumina C (ALC), D50: 0.013 ⁇ m) was mixed with the solution, and a resultant solution was stirred for 240 minutes. A resultant solution was filtered with a 1000-mesh metal gauze, and then 0.73 g of calcium carbonate was added and stirred for 240 minutes for neutralization. A resultant mixture was then defoamed under reduced pressure, and thus a coating liquid in the form of slurry was prepared.
• the coating liquid thus prepared is herein referred to as a coating liquid 2.
• the coating liquid 2 was left still for 1 hour at a room temperature, so that a dispersion state of components in the coating liquid 2 became moderately nonuniform.
• a layer A having a thickness of 10 ⁇ m was coated with the coating liquid 2, and thus a coating film was formed.
• the coating film was dried under an atmosphere at 50° C. and at a relative humidity of 70%, and thus an aromatic polymer, i.e., the para-aramid contained in the coating liquid 2 was deposited on the layer A.
• the coating film from which the aromatic polymer had been deposited was cleaned with water and dried, and thus a laminated porous film 2 in which a porous layer was stacked on the layer A was obtained.
• the laminated porous film 2 thus obtained is herein referred to as a nonaqueous electrolyte secondary battery laminated separator 2.
• a nonaqueous electrolyte secondary battery laminated separator 3 was prepared with use of a layer A and a layer B below.
• a polyethylene porous film (layer A) was prepared by an operation similar to that of Example 1.
• a coating liquid in the form of slurry was prepared by carrying out an operation similar to that of Example 2, except that a weight of fine powdery alumina to be mixed with the “para-aramid solution having a para-aramid concentration of 1.5% by weight” was changed to 6 g.
• the coating liquid thus prepared is herein referred to as a coating liquid 3.
• a laminated porous film 3 in which a porous layer was stacked on a layer A was obtained by carrying out an operation similar to that of Example 2, except that the coating liquid 3 was used instead of the coating liquid 2.
• the laminated porous film 3 thus obtained is herein referred to as a nonaqueous electrolyte secondary battery laminated separator 3.
• a nonaqueous electrolyte secondary battery laminated separator 4 was prepared with use of a layer A and a layer B below.
• a polyethylene porous film (layer A) was prepared by carrying out an operation similar to that of Example 1.
• a coating liquid in the form of slurry was prepared by carrying out an operation similar to that of Example 2, except that a weight of fine powdery alumina to be mixed with the “para-aramid solution having a para-aramid concentration of 1.5% by weight” was changed to 2 g.
• the coating liquid thus prepared is herein referred to as a coating liquid 4.
• a laminated porous film 4 in which a porous layer was stacked on a layer A was obtained by carrying out an operation similar to that of Example 2, except that the coating liquid 4 was used instead of the coating liquid 2.
• the laminated porous film 4 thus obtained is herein referred to as a nonaqueous electrolyte secondary battery laminated separator 4.
• a nonaqueous electrolyte secondary battery laminated separator 5 was prepared with use of a layer A and a layer B below.
• a polyethylene porous film (layer A) was prepared by carrying out an operation similar to that of Example 1.
• a coating liquid was prepared by carrying out an operation similar to that of Example 1, except that a alumina powder (available from Sumitomo Chemical Company, Limited, product name: Sumicorandom AA05, D50: 0.5 ⁇ m) was used instead of the organic filler (1).
• the coating liquid thus prepared is herein referred to as a coating liquid 5.
• One surface of the layer A was subjected to a corona treatment at 20 W/(m 2 /min).
• the surface of the layer A which has been subjected to the corona treatment was coated with the coating liquid 5 with use of a gravure coater.
• the coating film was dried to deposit CMC contained in the coating liquid 5, and thus a porous layer (layer B) was formed on the layer A.
• a laminated porous film 5 in which the layer B was stacked on one surface of the layer A was obtained.
• the laminated porous film 5 thus obtained is herein referred to as a nonaqueous electrolyte secondary battery laminated separator 5.
• a nonaqueous electrolyte secondary battery laminated separator 6 was prepared with use of a layer A and a layer B below.
• a polyethylene porous film (layer A) was prepared by carrying out an operation similar to that of Example 1.
• the polymer solution was taken in an amount of 1000 g and, to the solution, 3000 g of NMP, 23.4 g of calcium carbonate (available from Ube Material Industries, Ltd.), 60 g of particles (a) (fine powdery alumina (available from NIPPON AEROSIL CO., LTD., alumina C (ALC), average particle size: 0.013 ⁇ m)), and 60 g of particles (b) (alumina powder (available from Sumitomo Chemical Company,
• the coating liquid thus prepared is herein referred to as a coating liquid 6.
• a laminated porous film 6 in which a porous layer was stacked on a layer A was obtained by carrying out an operation similar to that of Example 2, except that the coating liquid 6 was used instead of the coating liquid 2.
• the laminated porous film 6 thus obtained is herein referred to as a nonaqueous electrolyte secondary battery laminated separator 6.
• Preparation of positive electrode A mixture obtained by mixing 6 parts by weight of acetylene black and 4 parts by weight of polyvinylidene fluoride (available from KUREHA CORPORATION) with 90 parts by weight of LiNi 1/3 Mn 1/3 CO 1/3 O 2 serving as a positive electrode active material was dispersed in NMP, and thus a slurry was prepared. The slurry thus obtained was applied uniformly to a part of an aluminum foil serving as a positive electrode current collector and dried, and then rolled to have a thickness of 80 ⁇ m with a pressing machine.
• polyvinylidene fluoride available from KUREHA CORPORATION
• the aluminum foil thus rolled was cut so as to obtain a positive electrode that had (i) a first portion on which a positive electrode active material layer was formed and which had a size of 40 mm ⁇ 35 mm and (ii) a second portion on which no positive electrode active material layer was formed, which had a width of 13 mm, and which remained on an outer periphery of the first portion.
• the positive electrode active material layer had a density of 2.50 g/cm 3 .
• Graphite powder serving as a negative electrode active material
• a slurry was prepared.
• the slurry thus obtained was applied to a part of a rolled copper foil, which served as a negative electrode current collector and had a thickness of 20 ⁇ m, and dried, and then rolled to have a thickness of 80 ⁇ m with a pressing machine.
• the rolled copper foil thus rolled was cut so as to obtain a negative electrode that had (i) a first portion on which a negative electrode active material layer was formed and which had a size of 50 mm ⁇ 40 mm and (ii) a second portion on which no negative electrode active material layer was formed, which had a width of 13 mm, and which remained on an outer periphery of the first portion.
• the negative electrode active material layer had a density of 1.40 g/cm 3 .
• the positive electrode, each of the nonaqueous electrolyte secondary battery laminated separators 1 through 6, and the negative electrode were stacked (arranged) in this order so that (i) the layer B of each of the nonaqueous electrolyte secondary battery laminated separators 1 through 6 and the positive electrode active material layer of the positive electrode come into contact with each other and (ii) the layer A of each of the nonaqueous electrolyte secondary battery laminated separators 1 through 6 and the negative electrode active material layer of the negative electrode come into contact with each other.
• the positive electrode and the negative electrode were arranged so that a main surface of the positive electrode active material layer of the positive electrode was entirely included in a range of a main surface of the negative electrode active material layer of the negative electrode (i.e., entirely covered by the main surface of the negative electrode active material layer of the negative electrode).
• nonaqueous electrolyte secondary battery member was put into a bag made of a laminate of an aluminum layer and a heat seal layer. Further, 0.23 mL of nonaqueous electrolyte was put into the bag.
• the nonaqueous electrolyte was prepared by dissolving LiPF 6 in a mixed solvent of ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate at a ratio of 3:5:2 (volume ratio) so that the LiPF 6 would be contained at 1 mol/L.
• the bag was then heat-sealed while pressure inside the bag was reduced, so that a nonaqueous electrolyte secondary battery was prepared.
• Nonaqueous electrolyte secondary batteries prepared with use of the respective nonaqueous electrolyte secondary battery laminated separators 1 through 6 are herein referred to as nonaqueous electrolyte secondary batteries 1 through 6.
• Each of the nonaqueous electrolyte secondary batteries 1 through 6 which have not been subjected to a charge-discharge cycle was subjected to four cycles of initial charge and discharge at 25° C.
• Each of the four cycles of initial charge and discharge was carried out (i) at a voltage ranging from 2.7 V to 4.1 V, (ii) with CC-CV charge at a charge current value of 0.2 C (where the terminal current condition was 0.02 C), and (iii) with CC discharge at a discharge current value of 0.2 C (where the value of an electric current at which a battery rated capacity defined as a one-hour rate discharge capacity was discharged in one hour was assumed to be 1 C; the same applies hereinafter).
• the “CC-CV charge” is a charging method in which (i) a battery is charged at a predetermined constant electric current and, (ii) after a certain voltage is reached, the certain voltage is maintained while the electric current is being reduced.
• the “CC discharge” is a discharging method in which a battery is discharged at a predetermined constant electric current until a certain voltage is reached (the same applies hereinafter). For each of the nonaqueous electrolyte secondary batteries 1 through 6 after initial charge and discharge, an AC resistance at 1 kHz after initial charge and discharge was measured by the foregoing method.
• AC resistance increase ratio (%) at 1 kHz through 100 cycles (55° C.) AC resistance at 1 kHz after 100 cycles ⁇ 100/ AC resistance at 1 kHz after initial charge and discharge (3)
• the nonaqueous electrolyte secondary batteries 1 through 4 produced in Examples 1 through 4 have AC resistance increase ratios (%) at 1 kHz through 100 cycles (55° C.) which are lower than those of the nonaqueous electrolyte secondary batteries 5 and 6 produced in Comparative Examples 1 and 2. It has been thus confirmed that the nonaqueous electrolyte secondary batteries 1 through 4 have improved long-term battery characteristics.
• the nonaqueous electrolyte secondary batteries 1 through 4 include the porous layers having bursting strengths which are 3.0 kPa or more and 22.0 kPa or less.
• the bursting strength falling within the above range indicates that the porous layer is tolerant of tensile stresses from all directions and does not excessively stretch, that is, the porous layer has moderate elasticity in all directions.
• the nonaqueous electrolyte secondary battery porous layer and the nonaqueous electrolyte secondary battery laminated separator in accordance with an embodiment of the present invention have a moderate elasticity in all directions, and it is therefore possible to follow expansion and contraction of an electrode (for example, a negative electrode) even in a case where charge and discharge of the nonaqueous electrolyte secondary battery have been repeated. As a result, it is possible to improve a long-term battery characteristic such as an AC resistance increase ratio after charge-discharge cycles.
• a nonaqueous electrolyte secondary battery porous layer in accordance with an embodiment of the present invention is usable for production of a nonaqueous electrolyte secondary battery having an excellent long-term battery characteristic.

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